Cracking and oxidizing petroleum oil to make gasoline and useful products of oxidation



. spirit.

' and Oxidizin described by Patented Dec. 2, 1924.

UNITED STATES PATENT OFFICE.

GARLETON ELLIS, OF MONTCLAIR, NEW JERSEY.

CRACKING AND OXIDIZING PETROLEUM OIL TO MAKE GASOLINE AND USEFUL PRODUCTS 0'! OXIDATION.

Ho Drawing.

To all whom it may concern:

Be it known that I, CAnna'roN Ennis, a citizen of the United States, and a resident of Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Cracking Petroleum Oil to make Gasoline and Use ul Products of Oxidation, of

a which the following is a specification.

This invention relates to a method of producing gasoline and other hydrocarbons from etroleum and also various products of oxidation which are derived from the union of oxygen with the products of cracking heavier oils.

The invention is concerned not only with the production of gasoline by cracking an oil but also the oxidation of some part of the products of cracking particularly the unsaturated components as for example the olefins or other unsaturated substances reduced by the cracking of heavy oils suc as petroleum oil, as halt, gi-lsonite, fats andreases and the like. While the invention as many modifications and the sources of raw material are varied the process will be m ans of the use of oil gas as an illustrative procedure.

While the treatment of cracked material will be more specifically set forth below, the processes of oxidation therein disclosed are equally applicable to the treatment of uncracked etroleum oils.

For this purpose heavy petroleum oil first purified by means of a desulfurizing a ent may be dropped into a heated pan an allowed to become volatilized, the gases and vapors being passed through an elon ated strongly heated retort or cracking tu so as to yield a high percentage of lighter hydrocarbons inc udmg unsaturated bodies. In some cases these may constitute a very substantial portion of the fixed gases or very light constituents as for example twenty-five to forty per cent. These gases and vapors may be carried through a condensing apparatus, h draulic seal and the like by means of whic the heavier components, tars etc. are removed. If desired the products may be passed through scrubbers or compressors to remove the heavier constituents which are not so easily condensed in the previous stage of condensation. Thus by these condensation steps light oils are obtained which may be rectified to yield gasoline or motor Application filed January 3, 1922. Serial No. 528,655.

In one form of the invention the residual gases and vapors may be then subjected to a purification process to remove sulphur compounds or to remove any other desirable constitutents in case these be present. huch gases and vapors contain a substantial percentage of propylene and butylene and analogous olefins and are well adapted for catalytic oxidation by treatment with air and contacting with catalytic material. The gases and vapors therefore are mixed with air and are introduced into a catalytic chamher where the mixture is brought into contact with a catalyzer such as a spiral of copper gauze or brass, iron or any other suit able catalytic material in the form of the metal as for example pieces of wire gauze or fra ments of the metal. As a substantial evolution of heat occurs on oxidation the use of a metal catalyzer for oxidizing com pounds having the high heat of combustion characteristic of petroleum hydrocarbons affords a desirable means of conducting away excess heat. Since the regulation of temperature, especially prevention of too high a temperature is quite important in the oxidation of petroleum the application of a fragmental catalytic mass of metal or material havin the heat conductivity of metal is a desira le means of assisting in the important factor of temperature control.

Compounds such as copper or chromium oxide iron vanadate, silver chromate, molybdenum compounds and the like also may be used. A composite catalyzer consisting of two elements having more than one stage of oxidation as for exam 1e iron and vana diam or chromium afi'or s a desirable catalytic body. Thus if fragments of iron are coated with chromium oxide or vanadium oxide or mixtures of these oxides the oxidize-- ing effect of the composite catalyzer is obtamed with the heat conductivity of a metallic base. It is also possible to support the catalyzer on any other suitable carrier if desired. For example in small apparatus where the heat evolution is not so important a factor pumice may be used. Such substantially non-conducting carriers may also be used in larger apparatus if suitable provision is made to absorb any excess heat.

For example a mixture of the gas thus obtained by cracking and containing a substantial percentage of olefins is mixed with air in guantity "somewhat in excess of that require to oxidize the olefins to form for example, ketones and the mixture is passed over a spiral of copper gauze which" is maintained at a temperature just below a low red heat. An incipient or low red heat is about 500 to 525 C. and I preferably do A IOt gfrmit the temperature to exceed 525 referably a black heat is employed 'ust below a low red heat or in the neighborood of 400 to 500 C. In some cases a temperature of below 400, as for example, between 200 and 400 may be employed. By using pressures of several atmospheres above atmospheric pressure lower temperatures may be employed to advantage. As for example at a pressure of 10 atmospheres a temperature 0 200 to 300 C. may be used in some cases. The products issuing from the catalytic chamber may be directly passed into water or may be first passed through a condenser and any condensable material first removed, thus any steam formed by the oxidation or present in the incoming air may be condensed and carry with it various water soluble products. Hydrocarbons also may condense and separate above the water layer. Steam may be used to control the temperature in the ,catal tic mass or when no catalyzer is employe as a means of preventing too violent reaction or explosion. The steam may however be omitted. In any event any water which has formed by the combustion may be collected to some extent at least by suitable condensation. Or the products from the catalytic or oxidation chamber may pass into water and the water soluble. substances thus collected. The residual gases may be assed into an oil scrubber or silica gel i desired; Or water washing may be a second sta e of operation or omitted entirely, oil scru bing or silica gel being used. Activated carbon may be used as an absorbing agent.

In the aqueous solution from the oxida tion will be found the alcohols, ketones, aldehydes, acids,'quinones and other water soluble products of oxidation which may be formed. These will vary with different conditions of operation and nature of the raw material.

In the present invention, in one phase at least, it is an object to utilize kerosene or hydrocarbons the major portion of which boil substantiall below 250 or 300 C. Kerosene is rea ly vaporized and is suit able for this phase of the invention. .Any petroleum hydrocarbon which is readily vaporizahle and boils below 300 C. may be used in carrying out this phase of the invention.

In em loying kerosene first purified by means 0 a desulfurizing agent it may for example be passed through a heated tube or cracked under ressure to produce asoline and gases. he gasoline is suitfiily collected and the gases employed. for the oxidation. Or the gasoline may be va orized admixed with air and submitte to oxidation. In the first procedure the kerosene may be passed through a heated tube at a. temperature of 500 to 700 (1., the products may be then passed through a condenser, the light portions submitted to catalytic oxidation or the entire mixture of cracked products maybe passed through the catalytic mass in admixture with air or an oxygen-containing as. All the air may be added at once or i? desired the air may be added at intervals within the catalytic mass. The air may be preheated by passing it about the catalytic chamber or the receptacle in which oxidation is in progress.

The regeneration of the heat developed in the operation is desirable and it is not necessary in all cases to utilize the heat for the purpose of preheating the incoming air or the incoming mixture of air and hydrocarbon vapors or gases. The heat may be utilized in other ways. The temperature may be kept below a low red heat or incipent red heat, that is below approximately 500 C. through the introduction of a lesser quantity of air than that which would serve to oxidize the entire body of hydrocarbons to alcohols, aldehydes, ketones, organic acids or whatever particular product was desired. The useof a quantity of air suflicient only to oxidize a minor portion of the hydrocarbons to the organic derivative desired is a feature of the present invention. If for example the gases and vapors are rich in olefins containing say ten to twenty per cent or more a quantity of air or oxygen or other oxygen-containing gas may be introduced which will provide the oxygen netessary to oxidize the olefins to for example acetic acid. On the other hand if dibasic acids such as oxalic, succinic, malic or maleic acids and the like are desired the oxygen is proportioned accordingly, keeping in mind the desirability of having always an excess of h drocarbon in the ex t gases and vapors. referably in these exit products I prefer to have present a very substantial roportion of hydrocarbons in a substantiaily unoxidized condition. Preferably such proportion is at least fifty per cent of the total products calculated as drocarbons and o'r'ganic bodies containing oxygen. This does not include the carbon monoxide, carbon dioxide, water etc In the case of vapors or gases which are free from olefins as for example still gases,

the olefins of which have been scrubbed in some manner to remove the olefins, the same proportions hold with res set to the amount of oxygen to employ. T e oxidation is to be carried out such that an abundance of hydrocarbon is present in the exit gases and va rs.

he oxidation of kerosene as referred to above carried out in this manner employing a catalyzer of vanadium oxide and a temperature of 300 to 400 C. yields aldehydes and fatty acids. A small amount of formaldehyde is produced and higher aldehydes. The treatment of the aqueous solution containing aldehydes and acids is preferably as follows: If the aldehyde is desired in the free state the solution is rendered neutral with caustic soda and distilled with steam. The aldehyde is carried over and the aqueous solution becomes practically odorless. The higher aldehydes may be employed in various ways for example they may be made to react with caustic soda to form a resinous substance. In one case a resin of this sort was reduced from kerosene and was obtains in the form of a light brown powder which could be melted to a resinous substance. The aldehydes also apparently polymerize during the oxidizing operation, to some extent.

The neutral solution containing the salts of organic acid may be rendered very slightly acid with sulphuric or phos horic acid and the organic acids distilled. Yn the case of the kerosene treatment referred to above a mixture of organic acids was obtained which were volatile with steam.

These evidently consisted largely of propionic, butyric acids etc. On blowing a strong current of steam through the aqueous operation as bleaching in substitution for oxalic acid etc. or may find uses in food products where an organic acid is desired to give a degree of acidity com arable with citric acid as for example in ma ing various beverages, syrups etc.

In some cases the catalyzer may be omitted the mixture of oil vapor and air with or without steam be passed throu h a heated tube the walls d which are sa stantially without catalytic efl'ect. The temperature is maintained below a red heat which avoids igniting conditions besides revents violent combustion or explosion.

emperatures of a red heat or a bright red heat such as have heretofore been recom mended are highly destructive to the products of oxidation and in the present invention are not used it bei necessary to maintain the temperature ow a low red heat. If the gaseous mixture is heated-to a point slightly below the ignition temperat'ure valuable oxidation reactions progress even though a catalytic substance is not present.

In one base of the invention the oxidation .of t e propyl group of immediate higher h drocarbon groups such as butyl, amyl an the like is especially considered. When petroleum oils are subjected to heat decomposition a substantial proportion of pro yl groups are rendered available by suc cracking treatment. It was commonly supposed that the break-down yielded ethylene, methane and the like in very large degree but it appears that the propyl roup is one of unusual stability and there ore is found in the products of cracking in the form of propylene, propane or hydrocarbons readily yieldin the propyl oup to oxidizin action. T is feature 0 my invention Is one which enables aldeh des such as propionic and butyric aldehy es to be prepared and makes possible the polymerizatlon or condensation of these aldehydes to produce suga substances. This condensation or po ymerization may occur during the oxidation under the heatin conditions so that in the products collected polymerized material will be obtained. In one case a product was obtained from kerosene which had the odor of maple an ar. In addition the oxidation may and 088 go to a further e that 05 producing propionic acid, butyrlc acid and the like so that the invention is also concerned with producing fatty acids higher in the series than acetic acid but more especiall the lower fatt acids above acetic whic are readily vo atile or easil volatilized with steam. These fatty aci s are of value in producing flavorin fruit essences and t e like and from petroleum oil by means of the process described compounds, artificial above esterified products have been obtained which have desirable fruity odors.

For example by neutralizing the acid water solution obtained by the oxidation of kerosene and distilling, aldeh des were separated which were ca ble 0 lymerization or condensation. n the residue after removal of aldehydes a lymerized substance was obtained and 0 salt of the organic acids. Thus com nds resembling sodium pro ionate and utyrate were derived and sated with ethyl alcohol and sulphuric acid producing a very agreeable odor somewhat suggestive of pears or pineapple but not distinctly the odor of either one. a r The ability to thus transform highly objectionable, evil-smelling petroleum oils such as kerosene into polymerized compounds and fruit flavors by the process aforesaid enables-such oils to be used in fields hitherto not considered available.

The present invention therefore is concernedm one aspect, with the cracking of petroleum oils to liberate immediate higher homol es m a very available form for air oxidation and conpropyl groups or verting such available and higher fatty aci mentioned.

The present invention thus opens the way of the petroleum refiner to produce fatty acids from petroleum which on esterfication yield esters having promising applications as artificial fruit flavors, in perfumes and in other fields heretofore remote from the petroleum industry.

Methods are already known by means of which, alcohols e. g. ethyl, propyl, butyl, amyl alcohols are prepared from still gases: suc methods having as the basis, the use of sul huric acid as an absorbing agent.

he petroleum refiner thus may produce alcohols on the one hand and fatty acids on the other and by suitable combination prepare at a relative] low cost a variety of esters heretofore quite costly.

The absorption method involving the use of sulphuric acid to which I have referred does not form any part of the present invention.

What I claim is 1. The process of cracking and oxidizing petroleum oil which comprises subjecting a volatilizable oil boilin below 300 C. to the action of a desulphurizing agent to remove sulphur, exposing the oil to a cracking temperature, incorporating air with the cracked products and heating to a temperature below a low red heat but of a degree sufficient to brin about oxidation; the amount of air empibyed being substantially less than that required for complete oxidation of the hydrocarbons present.

2. The process of cracking and oxidizing petroleum oil which comprises subjecting kerosene oil to the action of a desulphurizing agent to remove sulphur, exposing the oil to a cracking temperature, incorporating air with the cracked products and heating to a temperature below a low red heat but of a degree sufiicient to bring about oxidation; the amount of air employed being substantially less than that required for oxidation of all the hydrocarbons t resent.

3. The process of cracking and oxidizing etroleum oil which comprises subjecting erosene oil to a cracking temperature incorporating air with the cracked products and heating to a temperature below a low red heat but of a degree sufiicient to bring about oxidation; the amount of air employed being substantially less than that required for complete oxidation of the hydrocarbons present.

{4. The process of cracking-and oxidizing petroleum oil which com rises sulgecting a petroleum oil boilingbe ow 300' to a cracking temperature, incorporating air with the cracked products and heating to a temperature below a low red heat but of a groups into pro ionic s and other dies bodies from petroleum oil whi degree suiiicient to bring about oxidation; the amount of air employed being substantially less than that required for oxidation of all the hydrocarbons present.

5. The process of producing propyl products from petroleum oil which comprises cracking the oil whereby the propyl group is formed, bringing some portion 0 the products of cracking containing said propyl group into contact with an oxygen containing gas whereby propyl compounds are formed by reaction with the oxygen.

6. The )IOCQSS of producing propyl compounds w llCll comprises cracking petroleum oil whereby propyl groups are rendered available, passing some portion of the products of cracking through a heated zone in the presence of oxygen to yield oxygencontaining propyl compounds and in separating the utter from the other products.

7. The process of making propyl aldehyde which comprises cracking a petroleum oil to form available propyl groups, heating some portion of the products of cracking containing said propyl groups with oxygen in the presence of a catalyzer and collectin and separating the propyl aldehyde for-me 8. The process which comprises cracking kerosene to produce available propyl groups and reacting on the said propyl groups with oxygen at a temperature below a low red heat whereby oxygen-containing propyl compounds are produced.

9. The process of making polymerized c comprises cracking a petroleum oil to form available propyl groups, reacting on said propyl groups, reacting on said prop 1 groups with oxygen at a temperature be ow a low red heat whereby propyl aldehyde is formed and in allowing the aldehydeto polymerize.

10. The process of making a polymerized compound from kerosene which comprises exposing kerosene vapors to a cracking and oxidizing action whereby propyl aldehyde material is formed and polymerizes.

11. The process of making a mixture of fatty acids higher than acetic acid and consisting largely of propionic and butyric acids which comprises passing the products of cracking petroleum oil through a heated zone in the presence of oxygen whereb oxygen is caused to combine with the avai able propyl, butyl and other groups to form the mixed fatty acids aforesaid.

12. The process of producing oxidation products from petroleum oil which comprises heat treating petroleum ril to produce gases containing material amounts of olefins, and then sub'ecting the olefin containing gases to oxi ation, the amount of oxygen employed being sufficient to oxidize a minor portion only of the hydrocarbons.

13. The process of producing aldehyde Bil and acid products from petroleum oils which comprises heat treating thesaid oils to produce gases and vapors, oxidizin such gases and vapors to form acids and a1 eh de containing substances, resinifying said a dehydes, separating the resinous material, and then recovering the acidsfrom the residue.

14. The rocess of producing esters which comprises eat treating petroleum oils to gases.

CARLETON ELLISi' and liquid material, con- 10 from the still 15 Certificate of Correction.

n is hereby certified that in Letters Patent No. 1,517,968, gmnbed December 2,

upor; the a plicatmn of Carleton Ellis, of Monhcla1r,.Ncw Jersey, for an improvement in racking and oxidizing Petroleum Oil to Make Gasoline and Use f nets of Oxidation, errors appar in the printcd'specification requiring correction as follows: Paged, line 89, after the word oxide insert a comma; page 4 line 102, chain 9, afper the word grou a," first. occurrence, strike on; the

words reactmfion sald propyl. ups; and-t at the said Letters Patent should be read with Less corrections t erein that the same may conform to the record of jibe case in the Patent Oflice and sealed this 27th do of January, A. D. 1925. [mu] KARL FENNING,

Acting 00mm of Patents. 

